The combined effects of microbial inoculants (MI) and magnesium ammonium phosphate (MAP; struvite) on organic matter (OM) biodegradation and nutrients stabilization during biowaste composting have not yet been investigated. Therefore, the effects of MI and MAP on OM stability and P species during swine manure composting were investigated using geochemical and spectroscopic techniques. MI promoted the degradation of carbohydrates and aliphatic compounds, which improved the degree of OM mineralization and humification. MI and MAP promoted the redistribution of P fractions and species during composting. After composting, the portion of water-soluble P decreased from 50.0% to 23.0%, while the portion of HCl-P increased from 18.5% to 33.5%, which mean that MI and MAP can stabilize P and mitigate its potential loss during composting. These findings indicate that MI can be recommended for enhancing OM biodegradation and stabilization of P during biowastes composting, as a novel trial for the biological waste treatment.